The method of measuring diffusion coefficients using the twin-electrode thin-layer micrometer cell has been critically evaluated using the ferri-ferrocyanide couple in aqueous KCl as a model system. It has been demonstrated that precise measurements of steady-state currents and coulometric slopes can be made leading to reliable values for diffusion coefficients of soluble redox systems.
The following other systems were studied: Cu(II)/Cu(I) in 0.25M tetraethylallnonium perchlorate(TEAP-acetonitrile medium; ferroceneferricinim in three different solvents (acidified acetonitrile, N,N-dimethylformamide, propylene carbonate) with 0.1M TEAP as supporting electrolyte. Diffusion coefficients for the electroactive species were obtained, and electron-transfer characteristics of the redox systems were observed.
The dependence of the diffusion coefficients on viscosity was found to be in general agreement with the Stokes-Einstein relationship for the systems examined.
The kinetics of the reaction of ferricinium ion with oxygen was studied in a preliminary fashion. A second-order dependence on ferrocene concentration was found, with fractional order of dependence on oxygen.
","abstract_html":"<p>The method of measuring diffusion coefficients using the twin-electrode thin-layer micrometer cell has been critically evaluated using the ferri-ferrocyanide couple in aqueous KCl as a model system. It has been demonstrated that precise measurements of steady-state currents and coulometric slopes can be made leading to reliable values for diffusion coefficients of soluble redox systems.</p> <p>The following other systems were studied: Cu(II)/Cu(I) in 0.25M tetraethylallnonium perchlorate(TEAP-acetonitrile medium; ferroceneferricinim in three different solvents (acidified acetonitrile, N,N-dimethylformamide, propylene carbonate) with 0.1M TEAP as supporting electrolyte. Diffusion coefficients for the electroactive species were obtained, and electron-transfer characteristics of the redox systems were observed.</p> <p>The dependence of the diffusion coefficients on viscosity was found to be in general agreement with the Stokes-Einstein relationship for the systems examined.</p> <p>The kinetics of the reaction of ferricinium ion with oxygen was studied in a preliminary fashion. A second-order dependence on ferrocene concentration was found, with fractional order of dependence on oxygen.</p>","abstract_has_math":false,"creators":["Konopka, Stanley J."],"institution":null,"degree_name":"Doctor of Philosophy (PhD)","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Eugene E. Schrier","Walter E. Kaskan","Bruce McDuffie"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":1971,"date_issued":"1971-01-01T08:00:00Z","date_published":"1971-01-01T08:00:00Z","updated_at":"2026-07-24T01:10:16Z","subjects":["Electrochemical analysis","Diffusion","Twin-electrode thin-layer electrochemistry"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"https://orb.binghamton.edu/dissertation_and_theses/165","outbound_label":"Repository record","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Eugene E. Schrier","Walter E. Kaskan","Bruce McDuffie"]},{"key":"dc:creator","label":"Author","values":["Konopka, Stanley J."]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Dissertation"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Doctor of Philosophy (PhD)"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Electrochemical analysis","Diffusion","Twin-electrode thin-layer electrochemistry"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["https://orb.binghamton.edu/dissertation_and_theses/165"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["The method of measuring diffusion coefficients using the twin-electrode thin-layer micrometer cell has been critically evaluated using the ferri-ferrocyanide couple in aqueous KCl as a model system. It has been demonstrated that precise measurements of steady-state currents and coulometric slopes can be made leading to reliable values for diffusion coefficients of soluble redox systems.
The following other systems were studied: Cu(II)/Cu(I) in 0.25M tetraethylallnonium perchlorate(TEAP-acetonitrile medium; ferroceneferricinim in three different solvents (acidified acetonitrile, N,N-dimethylformamide, propylene carbonate) with 0.1M TEAP as supporting electrolyte. Diffusion coefficients for the electroactive species were obtained, and electron-transfer characteristics of the redox systems were observed.
The dependence of the diffusion coefficients on viscosity was found to be in general agreement with the Stokes-Einstein relationship for the systems examined.
The kinetics of the reaction of ferricinium ion with oxygen was studied in a preliminary fashion. A second-order dependence on ferrocene concentration was found, with fractional order of dependence on oxygen.
"]},{"key":"dc:title","label":"Title","values":["Diffusion coefficient measurements and other investigations using the methods of twin-electrode thin-layer electrochemistry"]}]}],"canonical_facts":{"dc:contributor":["Eugene E. Schrier","Walter E. Kaskan","Bruce McDuffie"],"dc:creator":["Konopka, Stanley J."],"dc:description.abstract":["The method of measuring diffusion coefficients using the twin-electrode thin-layer micrometer cell has been critically evaluated using the ferri-ferrocyanide couple in aqueous KCl as a model system. It has been demonstrated that precise measurements of steady-state currents and coulometric slopes can be made leading to reliable values for diffusion coefficients of soluble redox systems.
The following other systems were studied: Cu(II)/Cu(I) in 0.25M tetraethylallnonium perchlorate(TEAP-acetonitrile medium; ferroceneferricinim in three different solvents (acidified acetonitrile, N,N-dimethylformamide, propylene carbonate) with 0.1M TEAP as supporting electrolyte. Diffusion coefficients for the electroactive species were obtained, and electron-transfer characteristics of the redox systems were observed.
The dependence of the diffusion coefficients on viscosity was found to be in general agreement with the Stokes-Einstein relationship for the systems examined.
The kinetics of the reaction of ferricinium ion with oxygen was studied in a preliminary fashion. A second-order dependence on ferrocene concentration was found, with fractional order of dependence on oxygen.
"],"dc:identifier":["https://orb.binghamton.edu/dissertation_and_theses/165"],"dc:subject":["Electrochemical analysis","Diffusion","Twin-electrode thin-layer electrochemistry"],"dc:title":["Diffusion coefficient measurements and other investigations using the methods of twin-electrode thin-layer electrochemistry"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["Dissertation"],"thesis:degree_name":["Doctor of Philosophy (PhD)"]},"updated_at":"2026-07-24T01:10:16Z"}